Aluminium pigments

Abstract: Aluminium flakes coated with a film of molybdic acid in an amount of from 0.1 to 10% by weight in terms of Mo metal based on the weight of aluminium, and a phosphoric ester obtainable by an esterification reaction of a multifunctional epoxy compound with a phosphoric compound adsorbed to said film in an amount of from 0.05 to 5% by weight in terms of P element based on the weight of aluminium.

Description: The present invention relates to aluminium flakes, aluminium pigments which are used for producing water base metallic paints, and water base metallic paints and inks. Aluminium pigments, for example to be used for producing water base metallic paints and water base metallic inks, are described in several prior publications. For example, JP-B-59009729 discloses a process in which an aluminium pigment is treated with an aqueous solution containing phosphoric acid or its salt. According to this treatment, an aluminium pigment which inhibits the production of hydrogen gas sufficiently and has a good stability in paint can be obtained, but this treatment has defects in that the colour tone of the resulting paint film is spoiled by the treatment and in that whitening of the paint film occurs when the paint film is dipped in hot water due to the poor moisture resistance of the paint film. JP-B-85008057 discloses a process in which an aluminium pigment is treated with, for example, a phosphoric ester of lauryl alcohol. According to this treatment, an aluminium pigment having a stability in paint and good colour tone can be obtained, but an important defect of very poor paint film adhesion (adhesion between the pigment and a paint resin) is found. Techniques for the treatment of aluminium pigments with acid phosphoric esters modified with organic functional groups are also described in several prior publications, but each technique is unsatisfactory. JP-B-85015466 discloses a modification of phosphoric ester with an aromatic ring-containing functional group and an amino group, but this treatment cannot give a satisfactory improvement in the paint film adhesion. JP-A-61296072 discloses an introduction of a carboxyl group into the terminal of a modification group, but both the stability in paint and the paint film adhesion of the resulting aluminium pigment are not satisfactory. JP-B-89054386 discloses a prccess in which an aluminium pigment is treated with chromic acid. According to this treatment, an aluminium pigment which has good stability in paint and gives excellent colour tone to the resulting paint film can be obtained, and the paint film adhesion can be improved to a practically applicable level. However, since this treatment causes dissolution of aluminium flakes having fine particle sizes due to a high reactivity of the treatment, a fine aluminium pigment having an average particle size of D 50 < about 20 µm can hardly be produced. This is accompanied by serious industrial hygienic and environmental problems due to the use of a Cr(VI) compound. JP-A-61047771 (≡US-A-4621112) discloses a process in which a foam inhibitor comprising a reaction product of a specified epoxy resin with phosphoric acid is incorporated into a water-containing coating composition which contains a film-formable polymer, an untreated aluminium powder pigment and an aqueous dilution medium. The present invention seeks to provide an aluminium pigment which does not have the aforementioned defects involved in the prior art and which has an excellent balance of stability in paint, colour tone of the paint film, paint film adhesion and moisture resistance of the paint film. The inventors of the present invention have found that an aluminium pigment which is satisfactory in terms of the balance of stability in paint, colour tone of the paint film, paint film adhesion and moisture resistance of the paint film can be provided. Thus the present invention provides aluminium flakes coated with a film of molybdic acid in an amount of from 0.1 to 10% by weight in terms of Mo metal based on the weight of aluminium, and a phosphoric ester obtainable by an esterification reaction of a multifunctional epoxy compound with a phosphoric compound adsorbed to said film in an amount of from 0.05 to 5% by weight in terms of P element based on the weight of aluminium. The present invention also provides an aluminium pigment which comprises aluminium flakes as defined above and an aqueous or water-soluble carrier. The present invention additionally provides a method of preparing aluminium flakes as defined above comprising reacting aluminium flakes with ammonium molybdate in a water-soluble solvent and subsequently adsorbing the phosphoric ester to the reacted aluminium flakes. The present invention further provides a water base metallic paint or ink which comprises aluminium flakes as defined above. The present invention also provides a metallic paint film which comprises aluminium flakes as defined above. The present invention is characterized by the combination of a treatment with molybdic acid (hereinafter referred to as "first treatment") and a subsequent treatment (hereinafter referred to as "second treatment") with a phosphoric ester (hereinafter referred to as"stabilizing agent") which is formed by an esterification reaction of a multifunctional epoxy compound with a phosphoric compound. The combination of the first and second treatments as a characteristic feature of the present invention is novel, and though the aforementioned JP-A-61047771 discloses a process in which an aluminium pigment is contacted with a foam inhibitor comprising a reaction product of a specified epoxy resin with phosphoric acid, it does not teach a preliminary treatment of the aluminium pigment prior to said contact. The first treatment of the present invention comprises contacting an aluminium pigment with a first treatment agent in a water soluble solvent. Examples of usable water soluble solvents include ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether and isopropyl alcohol. The aluminium pigment to be subjected to the first treatment of the present invention is aluminium flakes produced by grinding or milling using a grinding agent in the presence of a grinding medium in a ball mill or an attritor mill. These flakes may have an average particle size (D 50 ) of preferably from about 1 to about 50 µm, particularly from about 10 to about 30 µm, from a view point of colour tone. As the grinding agent, higher fatty acids such as oleic acid, stearic acid, isostearic acid, lauric acid, palmitic acid and myristic acid are generally used, as well as aliphatic amines, aliphatic amides and aliphatic alcohols. As the grinding medium, a mineral oil having a high flash point such as mineral spirit or solvent naphtha is used. Desirably, the aluminium flakes may be washed in advance with a water soluble solvent which is used for the treatment so that they are easily wet with the treating solution. Especially, when the grinding medium is incompatible with the treating solution, it is effective to replace the grinding medium with an appropriate solvent in advance at the time of washing. Ammonium molybdate is desirable as the first treating agent. Usable ammonium molybdate is ortho-, meta- or para-molybdate. Alkali or alkaline earth metal molybdate, though soluble in water, is not preferable for the treatment of the aluminium flakes, because its alkaline strength is too high and, if the alkali or alkaline earth metal remains in the paint film, the remaining alkali or alkaline earth metal may affect the properties of the paint film. In the preparation of the treating solution, ammonium molybdate is preferably dissolved in a mixture of water and the water-soluble solvent so that it is contained at a concentration of a few percent or less (0.4% for example). When the aluminium flakes are reacted with the treating solution, the treating solution should be alkaline. In general, the pH of the treating solution is 7 to 10, preferably 7.5 to 9.5 and more preferably 8 to 9. When the pH is less than 7, the reaction with aluminum proceeds very slowly (dissolution of aluminium occurs at an acidic level which is out of the passive zone), and, when the pH is above 10, a rapid reaction occurs and, as a result, an aluminium pigment excellent in colour tone cannot be obtained. The first treatment is completed by removing the water and unreacted reactants from the reaction system. After completion of the first treatment, the reaction product is washed and filtered and then subjected to the second treatment. When cake of the aluminium pigment after the first treatment contains water, it is desirable to replace the water with the aforementioned water-soluble solvent prior to the second treatment. Storage at this stage is effected by dispersing the washed and filtered cake in, for example, the aforementioned water-soluble solvent. The amount of the film of molybdic acid formed by the first treatment is from 0.1 to 10% by weight in terms of Mo metal based on the weight of aluminium. When it is less than the lower limit, the stability in paint is poor and the inhibition of hydrogen gas production due to the reaction with water in the water base paint is insufficient. When it is above the upper limit, the film is too thick and, as a result, the colour tone thereof is impaired. A preferred range is from 0.1 to 3% by weight. The second treatment of the present invention comprises treating the first-treated aluminium pigment with a stabilizing agent. The stabilizing agent to be used in the second treatment is a phosphoric ester formed by the esterification reaction of a multifunctional epoxy compound with a phosphoric compound. This phosphoric ester is disclosed in Japanese patent applications nos 5-191745 and 5-191746 (JP-A-07/17986 and JP-A-07/17987). The phosphoric ester is, for example, selected from one of the following formulae: wherein:R 1 represents an alkyl or alkenyl group having 1 to 30 carbon atoms or is as hereinafter defined for Y 1 ; each X 1 is independently a group of formula -O-(CR a R b ) c CO- wherein R a and R b , which may be the same or different, is each hydrogen, a methyl group or an ethyl group and c is an integer of 4 to 8; each Y 1 is independently a hydroxycyclohexane backbone having a phosphate group of formula (1) and m 1 + m 2 + m 3 ..... m i is 0 to 30; wherein : R 2 is a residue of an organic compound having i active hydrogen atoms; each of n 1 , n 2 , n 3 ..... n i , which may be the same or different, is 0 or an integer of 1 to 30, with their total being 1 to 100; i is an integer of 1 to 10 and represents the number of active hydrogen atoms in R 2 , and each A is independently an oxycyclohexane backbone having a substituent X 2 of formula (2) where X 2 is a group selected from one of formulae (3) to (6) -CH=CH 2 wherein R' is hydrogen, an alkyl group, an alkylcarbonyl group or an arylcarbonyl group, with the proviso that the compound of formula [II] contains at least one group containing a phosphate group of formula (4) or (5); and wherein: R 3 is an alkyl or alkenyl group having 1 to 20 carbon atoms; each A' is independently an alkyl or alkenyl group having 1 to 20 carbon atoms; each X 3 is independently a group of formula -P (=O) (OH) 2 ; and i is an integer of 1 to 10. Typical examples of the phosphoric ester compounds of formula [I] include: a phosphoric acid addition product of an epoxy compound (Epolead GT400, manufactured by DAICEL CHEMICAL INDUSTRIES, LTD.) having the following formula (I-1) wherein a + b + c + d = 0; a phosphoric acid addition product of an epoxy compound (Epolead GT401, manufactured by DAICEL CHEMICAL INDUSTRIES, LTD.) having the following formula (I-2) wherein a + b + c + d = 1; a phosphoric acid addition product of an epoxy compound (Epolead GT403, manufactured by DAICEL CHEMICAL INDUSTRIES, LTD.) having the following formula (I-3) wherein a + b + c + d = 3; a phosphoric acid addition product of an epoxy compound (Epolead GT300, manufactured by DAICEL CHEMICAL INDUSTRIES, LTD.) having the following formula (I-4) wherein a + b = 0; a phosphoric acid addition product of an epoxy compound (Epolead GT302, manufactured by DAICEL CHEMICAL INDUSTRIES, LTD.) having the following formula (I-5) wherein a + b = 2; a phosphoric acid addition product of an epoxy compound (Celloxide 2081, manufactured by DAICEL CHEMICAL INDUSTRIES, LTD.) having the following formula (I-6) a phosphoric acid addition product of an epoxy compound (Celloxide 2083, manufactured by DAICEL CHEMICAL INDUSTRIES, LTD.) having the following formula (I-7) wherein n = 3; and a phosphoric acid addition product of an epoxy compound (Celloxide 2085, manufactured by DAICEL CHEMICAL INDUSTRIES, LTD.) having the following formula (I-8) A typical example of the phosphoric ester compound of formula [II] is a phosphoric acid addition product of an alicyclic epoxy compound (EHPE3150, manufactured by DAICEL CHEMICAL INDUSTRIES, LTD.) having the following formula wherein n 1 + n 2 + n 3 = 15. Typical examples of the phosphoric ester compounds of formula [III] include a phosphoric acid addition product of propylene glycol diglycidyl ether, a phosphoric acid addition product of diethylene glycol diglycidyl ether, a phosphoric acid addition product of trimethylolpropane triglycidyl ether and a phosphoric acid addition product of pentaerythritol tetraglycidyl ether. Processes for the production of the phosphoric esters to be used as the stabilizing agent in the second treatment of the present invention are described in the specifications of the aforementioned Japanese patent applications. Preferably, the second treatment of the present invention may be effected by dissolving the stabilizing agent in a polar solvent such as isopropyl alcohol, ethylene glycol, butyl cellosolve or propylene glycol monopropyl ether, adding a predetermined amount of the resulting solution to the first-treated cake put in a kneading device such as a mixer and then kneading the mixture. The stabilizing agent may be used in an amount of from 0.05 to 5% by weight, preferably from 0.1 to 1% by weight, in terms of the phosphorus content based on the weight of aluminium. A smaller amount than 0.05% by weight would not sufficiently inhibit gas production in the water base paints, and an amount larger than 5% by weight would cause reduction of the moisture resistance of paint films, thus entailing poor colour tone and paint film adhesion after a hot water resistance test. The aluminium pigment thus obtained by the second treatment has a double-layer structure in which the surfaces of the aluminium flakes are coated with a film of molybdic acid in an amount of from 0.1 to 10% by weight in terms of Mo metal based on the weight of aluminium, and the surface of the resulting film layer is further coated with the stabilizing agent in an amount of from 0.05 to 5% by weight in terms of phosphorus content based on the weight of aluminium. According to the present invention, the effects of the stabilizing agent used in the second treatment are further improved by the synergistic effect of the first treatment with molybdic acid and the second treatment with the stabilizing agent. Since the amount of the stabilizing agent to be added can be reduced greatly, defects which originate from the use of phosphorus-type additives, i.e. the decrease in the colour tone and adhesion of paint films after the hot water resistance test, can be controlled to a minimum level. This renders possible the production of an aluminium pigment having an unexpectedly excellent balance of properties including stability in paint, colour tone of paint film, paint film adhesion and moisture resistance of paint film. In addition the multifunctional epoxy compound used as one of the starting materials of the stabilizing agent maintains the adhesion between the aluminium pigment and a paint resin when baked in the paint film due to its strong cohesive force. This renders possible improvement of the poor film adhesion which is commonly observed when using the usual phosphorus-type compounds such as phosphoric esters. In the case of the process disclosed in JP-A-61047771 in which the foam inhibitor comprising a reaction product of an epoxy resin and phosphoric acid is contacted with the aluminium powder pigment, the effects of the inhibitor cannot fully be exerted because of the absence of the first treatment of the pigment. This entails a difficulty in obtaining an aluminium pigment having satisfactory properties such as stability in paint as well as colour tone and adhesion of paint films after the hot water resistance test (see Comparative Example 4 described later). The same publication limits the kinds of epoxy resins considerably in order to prevent the defects caused by the use of phosphorus-type compounds, but still insufficient properties result. According to the present invention, since the first treatment is applied to the aluminium pigment, such defects caused by phosphorus-type compounds can be reduced greatly, degree of influence of the structure of the epoxy compounds is small and the stabilizing agent can be selected from a broad range of compounds. The following Examples further illustrate the present invention. Reference Example 1: Preparation of stabilizing agent A (compound of formula II) A mixture consisting of 40 g of an epoxy resin (EHPE 3150, manufactured by DAICEL CHEMICAL INDUSTRIES, LTD.) and 40 g of propylene glycol monopropyl ether was added dropwise to a mixture consisting of 21.5 g of 100% phosphoric acid which had been prepared by mixing 100 g of 85% phosphoric acid with 40 g of diphosphorus pentoxide in that ratio and 26.0 g of propylene glycol monopropyl ether, taking about 1 hour for the dropwise addition while the temperature of the resulting mixture increased to about 90°C by the heat of reaction. After the exothermic reaction, the temperature was controlled at 90°C for about 2 hours. After completion of the reaction, the reaction mixture was cooled and its solid matter content was adjusted to 65% with propylene glycol monopropyl ether. The oxirane oxygen concentration in the crude reaction solution after cooling was found to be 0. Reference Example 2: Preparation of stabilizing agent B (compound of formula I) A mixture consisting of 40 g of an epoxy resin (Celloxide 2085, manufactured by DAICEL CHEMICAL INDUSTRIES, LTD.) and 16 g of propylene glycol monopropyl ether was added dropwise to a mixture consisting of 8.5 g of 100% phosphoric acid which had been prepared by mixing 100 g of 85% phosphoric acid with 40 g of diphosphorus pentoxide in that ratio and 25 g of propylene glycol monopropyl ether, taking about 1 hour for the dropwise addition. In a similar manner as the case of the stabilizing agent A, the temperature after the exothermic reaction was controlled at 90°C for about 2 hours. After completion of the reaction, the reaction mixture was cooled and its solid matter content was adjusted to 65% with propylene glycol monopropyl ether. The oxirane oxygen concentration in the crude reaction solution after cooling was found to be 0. Reference Example 3: Preparation of stabilizing agent C (compound of formula III) 40 g of neopentyl glycol diglycidyl ether was added dropwise to a mixture consisting of 25.6 g of 100% phosphoric acid which had been prepared by mixing 100 g of 85% phosphoric acid with 40 g of diphosphorus pentoxide in that ratio and 64 g of propylene glycol monopropyl ether, taking about 1 hour for the dropwise addition. In a similar manner as the case of the stabilizing agent A, the temperature after the exothermic reaction was controlled at 90°C for about 2 hours. After completion of the reaction, the reaction mixture was cooled and its solid matter content was adjusted to 65% with propylene glycol monopropyl ether. The oxirane oxygen concentration in the crude reaction solution after cooling was found to be 0. Reference Example 4: Preparation of stabilizing agent D (comparative compound) The compound of this Reference Example was prepared in accordance with Inventive Example 1 of JP-A-61047771. A mixture consisting of 42 g of an epoxy resin (Epikote 828, manufactured by Yuka Shell Epoxy K.K.) and 33.2 g of phenyl glycidyl ether was added dropwise to a mixture consisting of 24.6 g of 88% orthophosphoric acid and 0.2 g of triethylamine, taking about 1 hour for the dropwise addition while the temperature of the resulting mixture increased to about 120°C by the heat of reaction. After the exothermic reaction, the temperature was controlled at 110°C for about 2 hours. After completion of the reaction, the reaction mixture was cooled and its solid matter content was adjusted to 65% by diluting the mixture with propylene glycol monopropyl ether while the reaction product was still viscous. Thereafter, the reaction product was neutralized with 19.7 g of triethylamine. The oxirane oxygen concentration in the crude reaction solution after cooling was found to be 0. Examples 1 to 9 <First treatment of aluminium pigment> Aluminium flakes (Alpaste® 7675NS, D 50 = 14 µm, manufactured by Toyo Aluminium K.K.) were weighed so that 200 g in terms of aluminium was present, and placed in a 3 liter capacity beaker to which 1 liter of propylene glycol monomethyl ether was subsequently added and then stirred at 400 rpm to prepare a dispersion of aluminium flakes, and the whole was cooled to a liquid temperature of 18°C. To this was gradually added a reaction solution which had been prepared in advance by dissolving 5.0 g of ammonium paramolybdate in 200 ml of deionized water, subsequently stirring the resulting mixture at 400 to 450 rpm to carry out a reaction for 1 hour at pH 8.5 and at a liquid temperature of 15 to 20°C. The resulting reaction mixture was decanted with deionized water three times so as to remove ammonium ions and unreacted ammonium paramolybdate and then filtered through a glass filter with suction. Thereafter, the aluminium flakes on the filter were washed with propylene glycol monomethyl ether three times so as to completely remove the water and finally filtered with suction, thereby obtaining a first-treated aluminium pigment. <Second treatment of aluminium pigment> The thus obtained first-treated aluminium pigment was mixed with each of the stabilizing agents and butyl cellosolve in the respective amounts shown in Table 1 and subjected to 30 minutes of kneading in a mixer and then to 2 days of aging in a constant temperature oven of 50°C. The Mo content in each of the second-treated aluminium pigments was measured by ICP emission spectrophotometry, with the results shown in Table 1 in terms of Mo metal based on the weight of aluminium. The P content shown in Table 1 is a calculated value. Comparative Example 1 The aluminium flakes (Alpaste® 7675NS, D 50 = 14 µm, produced by Toyo Aluminium K.K.) as the starting material in the first treatment of Example 1 were used after replacement with propylene glycol monomethyl ether in order to be easily dispersed in the water base resin. Comparative Example 2 The aluminium flakes (Alpaste® 7675NS, D 50 = 14 µm, produced by Toyo Aluminium K.K.) as the starting material in the first treatment of Example 1 were subjected only to the first treatment. Comparative Example 3 Commercially available water base Alpaste® WXM 7675 (produced by Toyo Aluminium K.K.) was used. Comparative Example 4 The aluminium flakes (Alpaste® 7675NS, D 50 = 14 µm, produced by Toyo Aluminium K.K.) as the starting material in the first treatment of Example 1 were subjected only to the second treatment with the stabilizing agent D. Test Example Preparation of water base metallic paint The following materials: water-soluble acrylic resin neutralized with triethylamine (ALMATEX® WA 911, produced by MITSUI TOATSU CHEMICALS, INC.) 58.43 g melamine resin (Cymel® 350, produced by MITSUI CYANAMID) 8.80 g aluminium pigment (as metal Al) 6.00 g deionized water 80.00 g were thoroughly stirred and dispersed by hand followed by stirring by means of a disperser at 1,000 rpm for about 10 minutes. Then, its pH was adjusted with 10% triethylamine to be 8.6. Its viscosity was adjusted with deionized water to be 19 to 20 seconds by the determination using #4 Ford cup. Preparation of oily clear paint The following materials: acrylic resin (ACRYDIC® A-345, produced by DAINIPPON INK AND CHEMICALS INC.) 130 g melamine resin (SUPER BECKAMINE® L-117-60, produced by DAINIPPON INK AND CHEMICALS INC.) 50 g Solvesso® 100 70 g were dispersed by hand. The viscosity of the thus prepared clear paint was 20 seconds by the determination using #4 Ford cup. Coating method A steel plate which had been coated in advance with a primer was coated with the water base metallic paint using a SA-71 spray gun manufactured by IWATA TOSOKI KOGYO K.K. and an automatic air coating device Model 310741 manufactured by SPRAYMATION INC. so that the dried film had a thickness of 13 µm and subjected to 10 minutes of preliminary drying in an air oven of 90°C. Then the oily clear paint was coated so that the dried film had a thickness of 40 µm followed by baking to cure in the air oven of 160°C for 30 minutes, thereby obtaining test pieces. Items tested 1. Stability in paint A 80 g portion of the water base metallic paint which was not subjected to the viscosity adjustment was introduced in a flask, which was set on a water bath whose temperature was controlled to be 50°C to observe the cumulative volume of hydrogen gas produced for 10 days. The lower the cumulative volume of hydrogen gas, the higher the stability in paint. 2. Initial coating properties The colour tone of the test pieces after completion of coating, namely luster of the paint film (IV value), was determined using a colour measurement machine "ALCOPE", Model LMR-100, manufactured by KANSAI PAINT CO., Ltd. The paint film adhesion was determined by 6 ranks in accordance with the procedure of ASTM D3359 B. 3B or more is considered to be acceptable. 3. Resistance of paint film in hot water After the test piece was dipped in hot water of 50°C for 10 days, the adhesion of the paint film was determined in the same manner as described above to examine changes in the paint film adhesion before and after the 10 days of dipping in hot water of 50°C. Also, the change in the whitening degree of the dipped part was compared with the colour tone of the non-dipped part. The whitening degree was determined with the naked eye. The results were expressed by a double circle when no change in colour tone was observed, a single circle when only a slight change was observed, a triangle when judged borderline and a cross when a significant change was observed. Gas volume (ml/1 g Al) Coating properties initial after dipping in hot water IV value adhesion whitening adhesion Ex. 1 0.22 265 5B o ○ 5B Ex. 2 0.11 235 5B o ○ 5B Ex. 3 0.0 228 5B ○ 5B Ex. 4 2.9 252 5B o ○ 5B Ex. 5 0.0 258 5B ○ 5B Ex. 6 0.0 234 5B Δ 5B Ex. 7 0.0 252 5B ○ 5B Ex. 8 0.0 258 5B ○ 5B Ex. 9 0.0 234 5B Δ 5B Comp. Ex. 1 >20.0 271 5B o ○ 5B Comp. Ex. 2 6.4 228 5B o ○ 3B Comp. Ex. 3 0.76 267 5B × 5B Comp. Ex. 4 2.88 283 5B × 3B Comp. Ex. 5 5.5 238 5B Δ 3B

Claims: Aluminium flakes coated with a film of molybdic acid in an amount of from 0.1 to 10% by weight in terms of Mo metal based on the weight of aluminium, and a phosphoric ester obtainable by an esterification reaction of a multifunctional epoxy compound with a phosphoric compound adsorbed to said film in an amount of from 0.05 to 5% by weight in terms of P element based on the weight of aluminium. Aluminium flakes according to claim 1 wherein said phosphoric ester is selected from any one of the following formulae: wherein: R 1 is an alkyl or alkenyl group having 1 to 30 carbon atoms or is as hereinafter defined for Y 1 ; each X 1 is independantly a group of formula -O-(CR a R b ) c CO-wherein R a and R b , which may be the same or different, is each hydrogen, a methyl group or an ethyl group and c is an integer of 4 to 8; each Y 1 is independantly a hydroxycyclohexane backbone having a phosphate group of formula (1) and m 1 + m 2 + m 3 ..... m i is 0 to 30; wherein: R 2 is a residue of an organic compound having i active hydrogen atoms; each of n 1 , n 2 , n 3 ..... n i , which may be the same or different, is 0 or an integer of 1 to 30, with their total being 1 to 100; i is an integer of 1 to 10 and represents the number of active hydrogen atoms in R 2 ; and each A is independantly an oxycyclohexane backbone having a substituent X 2 of formula (2) wherein X 2 is a group selected from one of formulae (3) to (6) -CH=CH 2 wherein R' is hydrogen, an alkyl group, an alkylcarbonyl group or an arylcarbonyl group, with the proviso that the compound of formula [II] contains at least one group containing a phosphate group of formula (4) or (5); and wherein: R 3 is an alkyl or alkenyl group having 1 to 20 carbon atoms; each A' is independantly an alkyl or alkenyl group having 1 to 20 carbon atoms; each X 3 is independantly a group of formula -P(=O)(OH) 2 ; and i is an integer of 1 to 10. An aluminium pigment which comprises aluminium flakes as defined in claim 1 or 2 and an aqueous or water-soluble carrier. A method of preparing aluminium flakes as defined in claim 1 or 2 comprising reacting aluminium flakes with ammonium molybdate in a water soluble solvent and subsequently adsorbing the phosphoric ester to the reacted aluminium flakes. A water base metallic paint or ink which comprises aluminium flakes as defined in claim 1 or 2. A metallic paint film which comprises aluminium flakes as defined in claim 1 or 2.

Inventors: DAITO TERUMASA, FUJIWA TAKAAKI, MATSUFUJI TAKASHI, YAMAMOTO TAKASHI, DAITO, TERUMASA, FUJIWA, TAKAAKI, MATSUFUJI, TAKASHI, YAMAMOTO, TAKASHI
Applicants: DAICEL CHEM, TOYO ALUMINIUM KK, DAICEL CHEMICAL INDUSTRIES, LTD., TOYO ALUMINIUM KABUSHIKI KAISHA
Application year: 1994
Main classification: C09C1
IPC codes: C09C3, C09C1